CN109384921A - The preparation method of polyimide precursor composition and the polyimide film using it - Google Patents
The preparation method of polyimide precursor composition and the polyimide film using it Download PDFInfo
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- CN109384921A CN109384921A CN201810908279.1A CN201810908279A CN109384921A CN 109384921 A CN109384921 A CN 109384921A CN 201810908279 A CN201810908279 A CN 201810908279A CN 109384921 A CN109384921 A CN 109384921A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133305—Flexible substrates, e.g. plastics, organic film
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/13338—Input devices, e.g. touch panels
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The polyimide precursor composition of the publicly available preparation in flexible base board of the present invention, using its polyimides membrane preparation method and including the display devices of polyimide film.The polyimide precursor composition includes: mixed solvent contains 3- methoxyl group-N, N- dimethylpropionamide (M3DMPA) and N, N- dimethylpropionamide (DMPA)；And polyamic acid or polyimides.
Description
Technical field
It is related in more detail the present invention relates to polyimide precursor composition and using its polyimides membrane preparation method
And it can be used for the polyimide precursor composition of the preparation of flexible base board, using its polyimides membrane preparation method and comprising poly-
The display devices of acid imide film.
Background technique
Recently, to large area easy to accomplish and slim and light-weighted flat-panel monitor (Flat Panel can be carried out
Display；FPD demand) just increases.This flat-panel monitor has liquid crystal display device (Liquid Crystal Display；
LCD), Plasmia indicating panel (Plasma Display Panel；PDP), organic light-emitting display device (Organic Light
Emitting Display；OLED) etc..But previous flat-panel monitor uses glass substrate, therefore without flexibility, answers
It is limited with purposes.As display device of new generation, just actively research and development are replacing no glass substrate flexible as a result, use such as modeling
Material, foil etc. have the substrate of material flexible and flexible display apparatus (the Flexible for preparing in a manner of flexible
Display Device)。
Flexible display apparatus is usually with the preparation of the thin film transistor (TFT) of high temperature (TFT, Thin Film Transistor) process.
Process temperature can be different according to the type for semiconductor layer, insulating film and the barrier layer being included in device, in general, thin film transistor (TFT)
Manufacturing process needs 300 DEG C to 500 DEG C or so of temperature.But the polymer material that can bear this process temperature extremely has
Limit, it is main to use the well-known polyimides with outstanding heat resistance.Polyimides material not only has outstanding heat
Characteristic, moreover, soft and light weight, therefore, polyimide substrate as can instead of previous glass substrate plastic base by
Concern.
There are the various processes for preparing polyimide substrate, wherein most commonly used method is to utilize whirler (spin) or narrow
Polyamic acid (Polyamic acid) Polymer Solution is coated on glass with specific thickness by slot coating machine (slit coater)
Hot acyl is carried out by convection furnace (Convection Oven) or infra-red furnace (IR Oven) after glass carrier (Carrier Glass)
Imidization and solvent removal process and prepare polyimide substrate.Flexible display production process is in polyimide substrate
Form thin film transistor backplane, organic luminous layer etc. above to pass through light insulating film and remove (Laser Lift after manufacturing product
Off) method is separated from glass carrier.Polyimides material is easily bent, therefore in the state that substrate is fixed on to glass carrier
Lower carry out subsequent handling.Thin film transistor (TFT) or vapor deposition process carry out in higher temperature, therefore, if polyimides material and glass
The difference of the thermal expansion coefficient of glass carrier is big, then has glass carrier by curved worry, therefore, has similar thermal expansion system
Number is particularly important.
Polyamic acid Polymer Solution polymerize diamines (Diamine) in polar solvent and dianhydride (Dianhydride) comes
Preparation, as the polar solvent usually using dimethyl acetamide (Dimethylacetamide:DMAC,Boiling
Point: 165.1 DEG C), dimethylformamide (Dimethylformamide:DMF,Boiling point: 153 DEG C), N- methylpyrrole
Alkanone (N-Methylpyrrolidone:NMP,Boiling point: 202 DEG C) etc., still, these are environmental restrictions object,
It uses limited, it is therefore desirable to be replaced with other solvents.
Also, the hot-imide process for preparing polyimide substrate is determined according to hot setting (curing) process in furnace
Determine activity time (lead time), in order to save the time, carries out the shortening heating-up time, shortens the maintenance in each temperature step
The various trials such as time.Also, when progress high-temperature process (120 DEG C of processes start and 450 DEG C of solidification (cure) processes) and high speed
When dry, since solvent quickly volatilizees, defect generated in applicator surface, to improve this problem, attempts various methods.
Summary of the invention
The object of the present invention is to provide the environmentally friendly polyamides using the new mixed solvent for replacing environmental restrictions object solvent is sub-
Amine precursor composition.
Another object of the present invention is to provide prepared using the polyimide precursor composition with outstanding spy
The method of the polyimide film of property.
In order to realize the purpose, the present invention provides composition, and the composition includes: mixed solvent contains 3- methoxy
Base-N, N- dimethylpropionamide (M3DMPA) and N, N- dimethylpropionamide (DMPA)；And polyamic acid or polyimides.
Composition of the invention uses the new mixed solvent instead of environmental restrictions object solvent.It is molten by using newly mixing
Agent can shorten the preparation section time (lead time) of polyimide film by hot setting and rapid-curing cutback process.Also, pass through
Transmissivity and the good polyimide film of surface characteristic are obtained using the mixed solvent comprising 2 kinds of mutually different solvents of volatility.
Specific embodiment
Hereinafter, being carried out to the present invention detailed further.
Composition of the invention includes: mixed solvent, containing 3- methoxyl group-N, N- dimethylpropionamide (M3DMPA) and
N, N- dimethylpropionamide (DMPA)；And polyamic acid or polyimides.
The mixed solvent being used in the present invention is 2 kinds of different substances of volatility, is mixed with 3- methoxyl group-N, N- diformazan
Base propionamide (3-Methoxy-N, N-dimethylpropionamide；M3DMPA,Boiling point: 188.7
DEG C) and N, N- dimethylpropionamide (N, N-Dimethylpropionamide；DMPA,Boiling point: 174-176
DEG C), when carrying out high-temperature process, surface defect caused by the quick volatilization of solvent is prevented, and improve the transmission of polyimide film
Rate and surface characteristic.
3- methoxyl group-N, the N- dimethylpropionamide (M3DMPA): the mixing ratio of N, N- dimethylpropionamide (DMPA)
Rate (weight ratio) is 1:9 to 9:1, it is preferable that can be 3:7 to 7:3, for example, can be the weight ratio of 5:5.Wherein, if the 3- first
The usage amount of oxygroup-N, N- dimethylpropionamide (M3DMPA) is very few, then exist has film surface undesirable in rapid-curing cutback process
Problem, if the usage amount of 3- methoxyl group-N, the N- dimethylpropionamide (M3DMPA) is excessive, though then exist for film coating side
Face is advantageous, but has the problem of transmission reduction.
The polyamic acid used in the present compositions is compound in the molecule with amido and carboxyl, is logical
It crosses heating amido and carboxyl is reacted to form the macromolecule of imido grpup, diamine monomer and two can be made in the in the mixed solvent
Anhydride monomer is reacted to prepare.
P-phenylenediamine (p-Phenylenediamine:PPDA) can be used as the diamine monomer, 4,4'- diamino two
Phenylate (4,4'-Oxydianiline:ODA), 4,4'- methylene dianiline (MDA)s (4,4'-Methylene dianiline:MDA),
2,2'- dimethyl -4,4'- benzidine (m-Toli din；2,2'-Dimethyl-4,4'-Diaminobiphenyl), 1,
Bis- (4'- amino-benzene oxygen) benzene of 3- (1,3-BIS (4'-Aminophenoxy) benzene:TPE-R), and containing fluorine-based 2,
2'- bis- (trifluoromethyl) benzidine (2,2'-Bis (trifluoromethyl) benzidine:TFMB), the bis- [4- of 2,2-
(4- amino-benzene oxygen) phenyl] hexafluoropropane (2,2-BIS [4- (4-Aminophenoxy) Phe nyl]
Hexafluoropropane:HFBAPP), bis- (3- amino-4-hydroxylphenyl) the hexafluoro polyaniline propane (2,2-Bis (3- of 2,2-
Amino-4-hydroxy phenyl) hexafluoropropane:BIS-AP-AF), 1,3- diamino -2,4,5,6- phenyl tetrafluoride
(1,3-Diamino-2,4,5,6-Tetrafluorob enzene:DRFB), comprising sulfenyl 3,3'- diaminodiphenylsulfone (3,
3'-Diaminodiphen yl Sulfone:DDS), 4,4'- diaminodiphenyl sulfide (4,4'-Diamino
DiphenylSulfi de:ASD), bis- [4- (4- amino-benzene oxygen) phenyl] sulfone (Bis [4- (4-amino phenoxy) ph
Enyl] sulfone:BAPS), bis- [4- (3- amino-benzene oxygen) benzene] sulfone (2,2-Bis [4- (3-A mino phenoxy) of 2,2-
Benzene] Sulfone:m-BAPS) etc..Wherein, one kind or two or more monomer can be mixed to come using in order to ensure high heat resistance
Characteristic, it is appropriate that the p-phenylenediamine as fragrant (Aro matic) structures alone.
It, can as the dianhydride (Dianhdride) monomer it is appropriate that aromatic dianhydride (Dianhydr ide) compound
Use 3,3', 4,4'- benzophenone tetracid dianhydride (3,3', 4,4'-Benzophenone tetracarboxylic
Dianhydride:BTDA), pyromellitic acid dianhydride (Pyromellitic d ianhydride:PMDA), 3,3', 4,4'- biphenyl
Tetracarboxylic dianhydride (3,3'4,4'-Biphenyl tetr acarboxylicacid dianhydride:BPDA), 2,2- it is bis- (3,
The anhydrous dicarboxyphenyi of 4-)-hexafluoropropane dianhydride (2,2-Bis (3,4-anhydrodicarboxy phenyl)-
Hexafluoro propane dianhydride:6FDA), 2,3,3', 4- biphenyl tetracarboxylic dianhydride (2,3,3', 4-
Biphenyl t etracarboxylicacid dianhydride:a-BPDA), the double phthalic anhydride (4,4'- of 4,4'- oxygen
Oxydiphthalic Anhydride:ODPA), 3,3', 4,4'- diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride (3,3', 4,4'-
Diphenylsulfone-tetracarboxylic Dianhydride:DSDA), the bis- [4- (3,4- di carboxyl phenyloxy) of 2,2-
Phenyl] propane dianhydride (2,2-bis [4- (3,4-dicarboxy phen oxy) phenyl] propane dianhydride:
BPADA), 4,4'- is to double phthalic anhydrides (Hydroquinone diphthalic anhydride:HQDA) of benzene dioxy etc..
Wherein, can mix one kind or two or more monomer come using, in order to ensure high heat resistance characteristic, it is appropriate that 3,3', 4,4'- biphenyl
Tetracarboxylic dianhydride (3,3'4,4'-Biphenyl tetracarboxylicacid dianhydride:BPDA).
Composition of the invention can further include additive as needed.The additive can be multi-functional comprising epoxy
Substance can play the role of the defect for improving applicator surface together with mixed solvent.For example, the additive can be used by followingization
[chemical formula 1-1] ethylene glycol diglycidylether (Ethylene glycol diglycidyl ether) of formula expression [is changed
Formula 1-2] N, N- diglycidyl -4- glycidol oxo aniline (N, N-Diglycidyl-4-Glycidyloxy ani
Line), bis- ((2,3- glycidoxy) methyl) hexamethylene (the 1,4-Bis ((2,3- of [chemical formula 1-3] 1,4-
Epoxypropoxy) methyl) cyclohexane), [chemical formula 1-4] 2,2 '-[1,3- phenylene is bis- (Oxymethylene)] two rings
Oxidative ethane (2,2'- [1,3-Phenylenebis (oxymethylene)] dioxiran e), [chemical formula 1-5] 4,4'- methylene
Base bis- (N, N- diglycidylanilines) (4,4'-methyl ene bis (N, N-diglicidyl aniline)) etc., but
It's not limited to that, can will be used as additive comprising the multi-functional resin of epoxy.
Relative to the polyamic acid or polyimides of 100 parts by weight, can add described in 0.02 parts by weight to 1.2 parts by weight
Additive.Wherein, if the additive amount of the additive is very few, the problem of film surface sticks up can occur, if excessively, existing
The problem of decrease in transmission (less than 50%) of film.
The backward composition addition of the invention that the additive can dissolve in a solvent, the solvent of solubilising additive can be
Mixed solvent comprising 3- methoxyl group-N, N- dimethylpropionamide (M3DMPA) and N, N- dimethylpropionamide (DMPA), but simultaneously
It is not limited to this, in order to improve physical property, other kinds of solvent can be used.
[chemical formula 1-1]
[chemical formula 1-2]
[chemical formula 1-3]
[chemical formula 1-4]
[chemical formula 1-5]
In the present compositions, relative to the mixed solvent of 100 parts by weight, the polyamic acid or polyamides are sub-
Amine can be 5 parts by weight to 30 parts by weight, preferably 8 parts by weight to 20 parts by weight, it is highly preferred that can be 10 parts by weight to 15 weight
Part.Wherein, if the content of the polyamic acid or polyimides is very few, viscosity is low, in homogeneous thickness poly- therefore, it is difficult to obtain
Acid imide film, it is high because solvent, which quickly volatilizees, causes surface bad a possibility that when being put into high temperature furnace (bake), if described
The content of polyamic acid or polyimides is excessive, then viscosity is high, when carrying out slit coating, it is difficult to the thickness for adjusting film, from
And a possibility that forming relatively thick film, is high.
In the present compositions, the viscosity of composition can be 1000cP to 20000cP.In viscosity less than 1000cP's
In the case of, low molecule is relatively more, and mobility when coating is high, big in viscosity so as to form the thin Kapton of thickness
In the case where 20000cP, macromolecule is more, and mobility reduces, therefore forms relatively thicker thick film, to be difficult to obtain appropriate
The thickness of polyimide film.
Then, the preparation method of polyimide film of the invention is illustrated.
For polyimide film produced according to the present invention, firstly, using applicator (applicator) by the composition
Carrier substrate (carrier glass etc.) is coated on such as 400 μ m thicks (wet thickness).At this point, as carrier substrate, it can nothing
Especially limitation ground uses glass, metal substrate or plastic base etc., wherein it is preferable to use glass substrate, the glass substrate exists
To having outstanding thermal stability and chemical stability in the curing process of polyimide precursor, handled without additional mould release
Can also be easy by do not damage solidify after separate in a manner of the polyimide film that is formed.The working procedure of coating can be according to conventionally-coated
Method is implemented, specifically using whirl coating, rod-type coating process, roll coating method, air knife method, gravure method, reverse roll method, wet
Moisten roller method, scraper method, gunite, infusion process or brushing (brushing) method etc..
The composition can be so that thickness of the polyimide film finally prepared as display base plate with thickness appropriate
It spends in range and is coated on the upside of substrate.Specifically, after solvent evaporates and solidifies, 1 μm can be become with final thickness extremely
30 μm of amount coating.After the coating process, also optionally implement to be present in for removing before curing process
The drying process of solvent in composition.The drying process can be implemented according to conventional methods, specifically can be at 140 DEG C or less or 80
DEG C implement into 140 DEG C of temperature.If the implementation temperature of drying process is lower than 80 DEG C, the drying process time is elongated, if dry
The implementation temperature of process is higher than 140 DEG C, then quickly carries out imidizate and be difficult to form polyimide film in homogeneous thickness.
On the other hand, it is consumed for quite a long time by the curing process of hot-imide process, therefore, solidification need to be reduced
Activity time just can increase output.Accordingly, it is intended to coated substrate in the state that furnace without being cooled completely, after putting into
To shorten activity time.It in the present invention, can be in the cooling furnace being not over, for example, at 100 DEG C when carrying out curing process
Temperature in convection furnace in heated until 450 DEG C with 5 DEG C to 10 DEG C of heating rate per minute to prepare polyamides Asia
Amine film.The curing process can be heated to 300 DEG C to 450 DEG C of temperature according to circumstances to carry out.Also, the curing process can
By carrying out multi-step process according to the heat treatment of step within the scope of temperature as described above, for example, can be in 200 DEG C of temperature
Middle progress first time heat treatment carries out second of heat treatment in 300 DEG C of temperature, carries out third time in 350 DEG C of temperature
Heat treatment is to execute, and but not limited to this.Also, when carrying out the curing process, curing time is not particularly limited,
As an example, it is possible to implement 3 minutes to 60 minutes.
Also, after the curing process, in order to sub- by the acyl for improving polyimide based resin in polyimide film
Amination rate forms the polyimide film with outstanding physical property characteristic, also optionally implements subsequent heat treatment work
Sequence.The subsequent heat treatment process can be implemented 1 minute to 30 minutes in 200 DEG C or more or 200 DEG C to 450 DEG C of temperature.And
And the subsequent heat treatment process can be implemented 1 time, or can also implement 2 times or more multi-steps.Specifically, it is possible to implement
Including the first heat treatment in 200 DEG C to 220 DEG C temperature, the second heat treatment in 300 DEG C to 350 DEG C temperature and 400 DEG C to 450
3 steps of the third heat treatment in DEG C temperature.Then, base after cooling can be formed in from carrier substrate removing by conventional method
Polyimide film on plate is completed.
In the case where composition of the invention includes polyimides together with mixed solvent, to have executed imidizate
State therefore can prepare polyimide film by evaporating solvent after coating composition.For example, the evaporation of solvent can
It is executed with 200 DEG C or more of temperature heating, but not limited to this.
It can provide display base plate and device including the polyimide film.Specifically, the device can be for flexible
Property any solar battery (for example, flexible solar battery) of substrate, Organic Light Emitting Diode (OLED) illuminate (for example, soft
Property Organic Light Emitting Diode illumination), any semiconductor devices with flexible base plate or the Organic Electricity with flexible base plate
The flexible display device of electroluminescence device, electrophoresis device or liquid crystal display device (LCD) etc..
Hereinafter, by specific embodiment, the present invention will be described in more detail.Following embodiments are only used for illustrating this hair
Bright, the present invention is not limited to following embodiments.
[embodiment 1]Prepare polyimide precursor composition:
3- methoxyl group-N, N- dimethylpropionamide (M3DMPA) and N, N- dimethyl propylene are being mixed with 1:9 (weight ratio)
The in the mixed solvent of the 529.2g of amide (DMPA) is completely dissolved the p-phenylenediamine (PPDA) of 21.62g (0.2mol) at normal temperature
Later, 3,3', 4, the 4'- biphenyltetracarboxylic dianhydrides (BPDA) of 58.84g (0.2mol) are put into be reacted, are stirred 18 hours
After terminate, thus obtain include relative to the mixed solvent of 100 parts by weight 15 parts by weight polyamic acid (before polyimides
Body) composition.In order to confirm that producing high-molecular successfully carries out and whether can carry out filming, BrookField viscosity is used
Meter has detected the viscosity of composition, and the viscosity of acquired polyamic acid composition is 13500cps.
[embodiment 2]Prepare polyimide precursor composition:
The blending ratio of 3- methoxyl group-N, N- dimethylpropionamide (M3DMPA) and N, N- dimethylpropionamide (DMPA) is
In addition to this 3:7 obtains polyamic acid (polyimide precursor) composition by method same as Example 1.It is acquired
Polyamic acid composition viscosity be 13000cps.
[embodiment 3]Prepare polyimide precursor composition:
The blending ratio of 3- methoxyl group-N, N- dimethylpropionamide (M3DMPA) and N, N- dimethylpropionamide (DMPA) is
In addition to this 5:5 obtains polyamic acid (polyimide precursor) composition by method same as Example 1.It is acquired
Polyamic acid composition viscosity be 12500cps.
[embodiment 4]Prepare polyimide precursor composition:
The blending ratio of 3- methoxyl group-N, N- dimethylpropionamide (M3DMPA) and N, N- dimethylpropionamide (DMPA) is
In addition to this 7:3 obtains polyamic acid (polyimide precursor) composition by method same as Example 1.It is acquired
Polyamic acid composition viscosity be 13400cps.
[embodiment 5]Prepare polyimide precursor composition:
The blending ratio of 3- methoxyl group-N, N- dimethylpropionamide (M3DMPA) and N, N- dimethylpropionamide (DMPA) is
In addition to this 9:1 obtains polyamic acid (polyimide precursor) composition by method same as Example 1.It is acquired
Polyamic acid composition viscosity be 13400cps.
[embodiment 1-1 to 1-5]Prepare polyimide film:
According to the additive amount of the amount contrast table 1 of the polyamic acid elemental solid ingredient, to the polyamides obtained by embodiment 1
Amino acid composition mixing N, N- diglycidyl -4- glycidol oxo aniline (N, N-Diglycidyl-4-
Glycidyloxyaniline it) and is stirred to be prepared for coating liquid composition.Using applicator by prepared coating liquid
Composition is coated on glass carrier (carrier glass) with 350 μm of thickness (wet thickness), is to 450 DEG C in convection furnace
It is only heated with 8 DEG C of heating rate per minute to have carried out hot imide reaction.To the formalness of acquired polyimide film
Analysis and shown in table 1 is carried out with optical characteristics etc..
[embodiment 2-1 to 2-5]Prepare polyimide film:
According to the additive amount of the amount contrast table 2 of the polyamic acid elemental solid ingredient, to the polyamides obtained by embodiment 2
Amino acid composition mixing N, N- diglycidyl -4- glycidol oxo aniline, in addition to this, by with embodiment 1-1 phase
With method carry out hot imide reaction, and formalness to acquired polyimide film and optical characteristics etc. are analyzed
And it is shown in table 2.
[embodiment 3-1 to 3-5]Prepare polyimide film:
According to the additive amount of the amount contrast table 3 of the polyamic acid elemental solid ingredient, to the polyamides obtained by embodiment 3
Amino acid composition mixing N, N- diglycidyl -4- glycidol oxo aniline, in addition to this, by with embodiment 1-1 phase
With method carry out hot imide reaction, and formalness to acquired polyimide film and optical characteristics etc. are analyzed
And it is shown in table 3.
[embodiment 4-1 to 4-5]Prepare polyimide film:
According to the additive amount of the amount contrast table 4 of the polyamic acid elemental solid ingredient, to the polyamides obtained by embodiment 4
Amino acid composition mixing N, N- diglycidyl -4- glycidol oxo aniline, in addition to this, by with embodiment 1-1 phase
With method carry out hot imide reaction, and formalness to acquired polyimide film and optical characteristics etc. are analyzed
And it is shown in table 4.
[embodiment 5-1 to 5-5]Prepare polyimide film:
According to the additive amount of the amount contrast table 5 of the polyamic acid elemental solid ingredient, to the polyamides obtained by embodiment 5
Amino acid composition mixing N, N- diglycidyl -4- glycidol oxo aniline, in addition to this, by with embodiment 1-1 phase
With method carry out hot imide reaction, and formalness to acquired polyimide film and optical characteristics etc. are analyzed
And it is shown in table 5.
[comparative example 1-1 to 1-5]Prepare polyimide film:
3- methoxyl group-N, N- dimethylpropionamide (M3DMPA) is used only as solvent to prepare polyamic acid composition,
In addition to this, hot imide reaction has been carried out by method identical with embodiment 1-1 to 1-5, and sub- to acquired polyamides
Formalness and optical characteristics of amine film etc. are analyzed and are shown in table 6.
[comparative example 2-1 to 2-5]Prepare polyimide film:
N is used only as solvent, and N- dimethylpropionamide (DMPA) prepares polyamic acid composition, in addition to this, leads to
It crosses method identical with embodiment 1-1 to 1-5 and has carried out hot imide reaction, and to the external shape of acquired polyimide film
State and optical characteristics etc. are analyzed and are shown in table 7.
<Physical Property Analysis of polyimides>
[viscosity measurements]
Existed using rotary high consistency rotational viscosimeter (rich strangle in the U.S. flies (BrookField) company, Corn-Plate mode)
Measurement obtains average value after measuring in 25 DEG C of temperature 3 times.
[film thickness]
The thickness of film confirmed average value and standard after measuring 10 times using ultrasonic thickness measurement instrument (Qnix4500)
Deviation.
[transmission measurement]
Being averaged in 5 visible light regions is measured using optical measuring instrument (Nippon Denshoku company, COH-400)
It is measured after transmission and has obtained average value.
[mechanical properties-stress (Stress), deformation rate (Strain)]
In order to measure the mechanical properties of polyimide film, Ametek, Inc. (Ametek LLOYD is utilized
Instrument universal testing machine (UTM, Universal Test Machine)).Prepare the width of 5mm, the length of 70mm
After above film test piece, lever size (Grip To Grip size) is set as 30mm, rate of extension (Tension
Rate) it confirmed average value and standard deviation later with 10mm/min tachometric survey 10 times.
[table 1]
(3- methoxyl group-N, N- dimethylpropionamide (M3DMPA): N, N- dimethylpropionamide (DMPA)=1:9)
[table 2]
(3- methoxyl group-N, N- dimethylpropionamide: N, N- dimethylpropionamide=3:7)
[table 3]
(3- methoxyl group-N, N- dimethylpropionamide: N, N- dimethylpropionamide=5:5)
[table 4]
(3- methoxyl group-N, N- dimethylpropionamide: N, N- dimethylpropionamide=7:3)
[table 5]
(3- methoxyl group-N, N- dimethylpropionamide: N, N- dimethylpropionamide=9:1)
[table 6]
(3- methoxyl group-N, N- dimethylpropionamide=100%)
[table 7]
(N, N- dimethylpropionamide=100%)
From the table 1 to table 7 it is found that with mixed solvent is used, polyimide film it is in apparent good order and condition, and can present
50% or more transmissivity.But in the case where the input amount of additive is few, though transmission is outstanding, surface state can
Can be bad, in the case where putting into excessive additive, transmissivity is remarkably decreased less than 50%.
Also, 3- methoxyl group-N is being used alone without using mixed solvent of the invention, N- dimethylpropionamide
(M3DMPA) or in the case where N, N- dimethylpropionamide (DMPA), confirmed film surface state is bad, it follows that passing through
Composition of the invention includes that mixed solvent has the effect of that the surface state of polyimide film can be improved.
In particular, with quick heating rate, for example, if embodiment is with the feelings of 8 DEG C of heating rate progress rapid-curing cutback processing
Under condition, the composition using mixed solvent in the present invention has the effect of that prepared film surface is in good condition, on the contrary, making
With such as N, in the case where a kind of solvent of N- dimethylpropionamide (DMPA), it can confirm that the surface state of film is bad.
In turn, in terms of the standard deviation of film thickness, by using mixed solvent of the invention, the standard deviation of thickness is
1 or less, that is, the difference of thickness is little, thus has the effect of the excellent reliability of thickness when formation film.
In terms of stress (Stress) and deformation rate (Strain), using mixed solvent of the invention, partially
Difference is respectively 10 or less, 1 hereinafter, the mechanical property of the polyimide film prepared as a result, using mixed solvent is not generated greatly
Variation, it may thus be appreciated that the excellent reliability of polyimide film.
Claims (6)
1. a kind of composition, characterized by comprising:
Mixed solvent contains 3- methoxyl group-N, N- dimethylpropionamide and N, N- dimethylpropionamide；And
Polyamic acid or polyimides.
2. composition according to claim 1, which is characterized in that relative to the mixed solvent of 100 parts by weight, include
The polyamic acid or polyimides of 5 parts by weight to 30 parts by weight.
3. composition according to claim 1, which is characterized in that also comprising being selected from by ethylene glycol diglycidylether, N,
Bis- ((2,3- glycidoxy) methyl) hexamethylenes of N- diglycidyl -4- glycidol oxo aniline, 1,4-, 2,2 '-[1,
3- phenylene is bis- (Oxymethylene)] diepoxide for example and 4,4' methylene bis (N, N- diglycidylaniline) composition
One kind or two or more additive in group.
4. composition according to claim 3, which is characterized in that relative to the polyamic acid of 100 parts by weight or poly-
Acid imide, the additive comprising 0.02 parts by weight to 1.2 parts by weight.
5. composition according to claim 1, which is characterized in that include the 3- methoxy with the weight ratio of 3:7 to 7:3
Base-N, N- dimethylpropionamide and N, N- dimethylpropionamide.
6. composition according to claim 1, which is characterized in that viscosity is 1000cP to 20000cP.
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| KR1020170102491A KR20190017527A (en) | 2017-08-11 | 2017-08-11 | Polyimide precursor composition and method for producing polyimide film using the same |
| KR10-2017-0102491 | 2017-08-11 |
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| CN112271400A (en) * | 2020-09-01 | 2021-01-26 | 广州天赐高新材料股份有限公司 | Novel application of amide compound |
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| KR102202484B1 (en) | 2019-04-23 | 2021-01-13 | 피아이첨단소재 주식회사 | Polyimide film, flexible metal foil clad laminate comprising the same and manufacturing method of polyimide film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015232688A (en) * | 2014-05-15 | 2015-12-24 | Jsr株式会社 | Radiation-sensitive resin composition, insulation film, and method for producing the same, and organic el element |
| CN106928707A (en) * | 2015-12-31 | 2017-07-07 | 株式会社东进世美肯 | Polyimide polymer composition, method for producing same, and polyimide film |
| CN106947080A (en) * | 2015-12-31 | 2017-07-14 | 东进世美肯株式会社 | Kapton preparation compositions and preparation method thereof and the preparation method using its Kapton |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015232688A (en) * | 2014-05-15 | 2015-12-24 | Jsr株式会社 | Radiation-sensitive resin composition, insulation film, and method for producing the same, and organic el element |
| CN106928707A (en) * | 2015-12-31 | 2017-07-07 | 株式会社东进世美肯 | Polyimide polymer composition, method for producing same, and polyimide film |
| CN106947080A (en) * | 2015-12-31 | 2017-07-14 | 东进世美肯株式会社 | Kapton preparation compositions and preparation method thereof and the preparation method using its Kapton |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112271400A (en) * | 2020-09-01 | 2021-01-26 | 广州天赐高新材料股份有限公司 | Novel application of amide compound |
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| KR20220137595A (en) | 2022-10-12 |
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